Baldwin subsequently appeared as Richard Gere's hapless partner and accomplice in "Internal Affairs" and as a death-defying, womanizing medical student in "Flatliners" (both 1990) before landing a leading role as a rookie fireman in Ron Howard's "Backdraft" (1991). He worked with some of contemporary Hollywood's most intriguing leading ladies in two very different 1993 features: as a male escort involved in a triangle with two estranged lesbian lovers (Kelly Lynch and Sherilyn Fenn) in the romantic comedy "Three of Hearts" and as a wealthy bachelor involved with Sharon Stone in the thriller "Sliver".

A small-scale critical hit and a big-scale bomb marked 1995 for Baldwin. He starred in Joshua Brand's well-received dark comedy "A Pyromaniac's Love Story", as one third of an unhealthy triangle with Sadie Frost and John Leguizamo. Later that year, he supported supermodel Cindy Crawford in her film debut, the ill-advised actioner "Fair Game". Baldwin's penchant for odd little projects was also displayed in "Curdled" (1996), where he played a sexy serial killer obsessed over by the heroine.

In 1995, Baldwin married singer-actress Chynna Phillips.